Process for purification of polluted water



Patented Nov. 21, 1933 UNITED STATES PATENT OFFICE Oliver M. Urbain, Columbus, Ohio, assignor to Charles H. Lewis, Hamster, Ohio No Drawings.

Application April 19, 1938 erial No. 666,934

8 Claims. (Cl. 210-2) This invention relates to a process for water purification.

, Heretofore much work has been done in the fleld of removing suspended and colloidal matter 6 irom polluted waters. Some attention has been devoted to the elimination of oxygen consuming organic compounds present in true solution in the waste waters. But, for the most part, processes relating to the latter field have been limited 10 in characterand uneconomical in practice.

The present invention is concerned primarily with the provision of an economical and practical process ior the elimination of the oxygen consuming compounds which are present in organic l5 waste waters in a state oi true solution.

The oxygen consuming compounds which are present in a state of true solution in waste waters may be properly classified in six major groups. It is the purpose oi the present invention to provide a process for the complete elimination oi all oi the organic compounds falling in these groups. The removal of such compounds by the present invention is effected by stoichiometric reactions.

The six groups oi oxygen consuming organic compounds present in waste waters in true solu tion are as follows:- v

Group 1.-Organic acids, R.COOH in which R equals any hydrocarbon radical, substituted or unsubstituted, or hydrogen.

Group 2.--Mercaptans; R.SH, in which R equals any hydrocarbon radical either substituted or unsubstituted.

Group 3.--Alcohols, R.OH, in which R equals any hydrocarbon radical either substituted or unsubstituted.

Group 4.-Amines, R..NH, in which R equals any hydrocarbon radical either substituted or unsubstituted.

Group 5 .--Aldehydes, R..CHO. in which R equals hydrogen or any hydrocarbon radical either substituted or unsubstituted.

Group 6.-Ketones, R.CO.R, in which R equals any hydrocarbon radical either substituted or unsubstituted.

The merit and simplicity oi the process resides in the fact that it is only necessary to incorporate two extraneous reagents into the waste water in order to eflect the elimination of all polluting materials oi the above six groups.

Aiter extensive experimentation I have discovered that it is possible to eiiect a quantitive reaction between carboxylic acids oi gr p 1 above and the (thionylamino) acyl halides. The reaction products are (acylamino) acid halides and S0:- The reaction product (acylamino) acid halide will react quantitively with the alcohols, the mercaptans and the amines.

The first reaction, namely, that between? the carboxylic acid and the (thionylamino) acyl halide occurs with the solution at a pH at or go below 7. l The subsequent reactions afiecting the alcohols, mercaptans and amines only occur when the solution has a pH of 8 or above, preferably around pH 9. Therefore, after the first reaction I add sodium hydroxide,,NaQH, to raise the pH 55 of the solution. The NaOH reacts with the SO: which, it will be observed, was a product of the first reaction, forming sodium bisuliite NaHSOa. The sodium bisulfite in turn reacts quantitively with the ketones and aldehydes. Thus, by the addition of the first reagent, i. e., (thionylamino) acyl halide and the second reaction, sodium hydroxide, it is possible to eflect a succession of reactions, producing reaction products which act to eliminate all of the six major groups oi the organic compounds listed above.

If carboxylic acids are present in an amount adequate to form with the (thionylamino) acyl halide employed suflicient (acylamino) acid halide to react with all of the alcohols, mercaptans and g0 amines present, then further addition 0! carbqxylic acid is unnecessary. Ii, however, insuflicient'carboxylic acid is present in the waste, it is necessary to make up thevdeilciency by the addition of a cheap carboxylic acid such as acetic g5 acid. Likewise, if the basic reaction does not supply suflicient sulfur dioxide to form suflicient NaHSOa to react with all oi the aldehydes and ketones present, it may be necessary to make up the deficiency by the addition of more S0: or more NaHSOa.

In each instance the reagents are employed in gram molecular equivalents. The basic reaction, (thionylamino) acyl halide and carboxylic acid, takes place at pHs below pH 7.0. The following reactions, five in number, take place at pH's above pH 7.0, preferably at pH 8.0 to 10.0, in a medium alkaline with caustic soda. Very little caustic soda is required as it lonizes very strongly.

The general formula: tor the (thionylamino) acyl halides is as iollows:- I

A equals carbon atom, sulfur atom, phosphorus atom, or arsenic atom.

1,935,964 X equals any halide atom. Cl Ongen is attached to A in one or more atoms. 1 The general reactions for the six groups above listed are as iollowsz- Nncocm+ cimsn= NHoocm+Hci am mea t e... i e

I n o B\ R COOH R l 80; P 0 aoebenme cactiido E 3 c1 lJ-ofln 3. =0 =0 agy l halide a i i i Ziiifiiil d i i de v NBC 0011. canon NHCOCH|+HCI o o l 1 n x s R tamid be 1 th 1 th '1 h dro- 2. B B"-BH B 4' Ex Hoe chlorfde my a l co ol o-ao tan iidoch loric \NC-B' O BI bOllZOilte acid 8 A .ci ,7 mum.

' 4. =0 =0 diulld e meant $223532) 2 31?- Nn0oom+cmNm= NHCOCH: HCl

/Lx ei-ter s ter n 0 I. I R on H a a acid r 6. so. NaOH =Nerrso. 5 1i 8 re wee see,

ha] 0 8 y 0 (mlamino) alcohol (gird: an 1am: o H

o. NeHso,+cm.cn,.oH,.cHo=cn..on,.0H,.hH-so..Ne o O n sodium butraldehyde butraldehyde sodium r I bisulilte bisulfite 1-x l-rt-a": 0H 11o B 1. NaHSO;+GHa.C0.CHr.CHr=CHt-( JCHrC r \fl I om:

A a a E z-butanone zbutfigtrlrliiistgdium lamlno hmln bstituted hal ah ide a y no) a fi In carrying out the process'one must first de- 116 termine the total amounts or the following m I groups of compounds present, carboiwlic acids, gmaf'm equals hydrogen or any alcohols, amines, mercaptans, aldehydes,ketones.

The reaction 01' the so, formed in the first reh quantity (acylamim) acid halide 120 action above and the NaOH added forms sodium wired to react with the total ammmts of bisulfite NaHSOa which enters into reaction with amines and memaptans Present 15 the fldemdes and ketone as computed. From this figure one can compute according to the first reaction the amount or a r on (thionylamino) acyl halide required to produce p the quantity of (acylamino) acid halide com- "I Nmso' latqxmmm puted above. This quantity of (thionylamino) H n acyl halide is added to the waste and it is agitated (hYdmWmlmag) for about five minutes. It there is present insufllcient carboxylic acids to react with all the w i a (thionylamino) acyl halide employed the de- 0==o 0' ficiency is made up by adding' the required 3/ \solNa amount of a cheap carboxylic acid, such as acetic m km mum to acid. During the above stage of the processthe v I m Mammy om pH is maintained below pH 7.0. Aiter the agita- 335 As stated, the first reaction takes place at all tion period is complete and while agitation conpHs below pH 7.0, and the remaining reactions tinues, I add sodium hydroxide in an amount take place at all pH's above pH 31.0, preferablyat suflicient to react with all 01' the sulfur dioxide pH 8.0 to 10.0. I released in the first reaction and sumcient exmmowm 2 81m exemplary aw using cess to raise the pH to pH above 8. The agi 4 M mt tion is continued tor about 8 minutes more after J which the liquid is passed into sedimentation l a 01 V basins. A conventionalcoagulant may be added 1, o x Just before passing the liquid into the sedimentation basins if desired N50 omcoon= NHOQC I l-S I Having thus described my invention, what I claim is:-- I

V 1. A process for eliminating the oiwgen cono-thion hmhobem i lmo o-eoetunldobenzoyi m s ommic compounds present in'true soluchloride -tion in organic waste waters comprising treating the waste water containing such compounds with an (thionylamino) acyl halide.

2. A process for eliminating ongen consuming organic compounds including alcohols, amines and mercaptans from waste water in which such compounds are present in true solution comprising reacting with such compounds an (acylamino) acid halide.

3. A process for eliminating oxygen consuming organic compounds including alcohols. amines and mercaptans from waste water in which such compounds are present in true solution comprising reacting with such compounds an (acylamino) acid halide tormed in situ.

4. A process for eliminating oxygen consuming organic compounds including alcohols, amines and mercaptans from waste water in which such compounds are present in true solution comprising reacting with such compounds an (acylamino) acid halide formed in situ by reaction of a carboxylic acid and an (thionylamino) acyl halide.

i. A process for eliminating oxygen consuming organic compounds including carboxylic acids, alcohols, amines and 'mercaptans from waste water in which said compounds are present in true solution comprising first reacting a (thionylamino) acyl halide with carboiwlic acid in an amount adequate to form (acylamino) acid halide in the solution sufiicient to react with all the alcohols, amines and mercaptans present in the waste water, effecting the first reaction with the pH of the solution at or below '1 and efiecting the subsequent reactions with the solution at a pH above 8.

6. A process for eliminating oxygen consuming organic compounds, present in true solution in organic waste waters, including carboxylic acids,

alcohols, amines, mercaptans, aldehydes and ketones, comprising first reacting an (thionyiamino) acyl halide with carboxylic acid in the solution in sufiicient amount to form in the solution (acylamino) acid halide adequate in amount to react with all alcohols, mercaptans and amines in the liquid, effecting the first reaction with the solution at a pH of approximately '7 and effecting the subsequent reactions with the solution at a pH above 8, maintaining the solution at a pH above 8 by adding thereto sodium hydroxide and utilizing the sodium bisulfite formed in the solution by reaction 0! the NaOH and the S0: released by said first reaction to react with the aidehydes and ketones in the waste water.

7. A process for eliminating omgen consuming organic compounds including organic acids, mercaptans, alcohols and amines from waste waters in which said compounds are present in true solu- Hon comprising introducing to the waste water a reagent capable oi reacting with at least one of said compounds to produce a reaction product capable of reaction with each of the remaining compounds.

8. A process for eliminating by stoichiometric reaction oxygen consuming compounds including organic acids, mercaptans, alcohols, amines, aldehydes and ketones from waste water in which said compounds are present in true solution comprising introducing a reagent capable of reacting with the organic acids while the solution is maintained at a pH below '1 to form reaction products in the solution available as reagents for effecting reaction with the remaining oxygen consuming compounds when the pH 01' the solution is raised above pH 8 by addition 01' NaOI-I thereto.

OLIVER M. URBAIN. 

